Triphenylphosphine mono and dimethoxy tri-sodium sulphonates

ABSTRACT

Process for the preparation of octa-2,7-dienyl-1-amine by telomerization of butadiene with ammonia in a two-phase system in the presence of hydrophilic palladium complexes, characterized in that octa-2,7-dienyl-1-amine and octa-1,7-dienyl-3-amine are isolated separately from one another from the reaction mixture present after telomerization, and the octa-1,7-dienyl-3-amine isolated in this way is subjected to an isomerization reaction to form octa-2,7-dienyl-1-amine, and also novel triphenylphosphine mono- and dimethoxytri(sodium sulphonates) and the use of triphenylphosphine trimethoxytri(sodium sulphonates), triphenylphosphine trimethyltri(sodium sulphonates) and triphenylphosphine trifluorodi- and tri(sodium sulphonates) as ligands for the preparation of palladium complexes.

This is a divisional application of U.S. Ser. No. 09/257,801, filed Feb.25, 1999, now U.S. Pat. No. 6,051,738.

FIELD OF THE INVENTION

The present invention relates to an improved process for the preparationof octa-2,7-dienyl-1-amine by telomerization of butadiene with ammoniain a two-phase system, subsequent isolation of octa-2,7-dienyl-1-amineand octa-1,7-dienyl-3-amine from the reaction mixture and isomerizationof the octa-1,7-dienyl-3-amine to give octa-2,7-dienyl-1-amine. Thepresent invention further relates to novel triphenylphosphine mono- anddimethoxytri(sodium sulphonates) and to the use of triphenylphosphinetrimethoxytri(sodium sulphonates), triphenylphosphinetrimethyltri(sodium sulphonates) and triphenylphosphine trifluorodi- andtri(sodium sulphonates) as ligands for the preparation of palladiumcomplexes.

BACKGROUND OF THE INVENTION

Octadienylamines are used, for example, as intermediates for thepreparation of octylamines, which in turn are required, for example, forthe preparation of fabric softeners, corrosion inhibitors, flotationauxiliaries and emulsifiers. For these purposes, octa-2,7-dienyl-1-aminein particular is of interest.

In the telomerization of butadiene and ammonia, complex reactionmixtures are usually produced which, in addition toocta-2,7-dienyl-1-amine, contain considerable amounts ofocta-1,7-dienyl-3-amine and secondary and tertiary octadienylamines.

From EP-A 773 211, it is known to carry out the telomerization ofbutadiene and ammonia in a two-phase system and to use as catalystsmixtures of palladium compounds and phosphorus compounds which improvethe solubility of the palladium compounds in water, for examplesulphonated triphenylphosphines.

Reaction mixtures containing octa-2,7-dienyl-1-amine (1),octa-1,7-dienyl-3-amine (2) and secondary octadienylamines (3) areproduced. (1) forms in selectivities of from 40 to 56%, (2) inselectivities of from 28 to 43% and (3) in selectivities of up to 10%.The reaction mixtures were not worked up.

According to EP-A 816 308, the complex compounds used as catalysts forsaid telomerization contain, as central atom, a transition metal and atleast one tris(hydroxyalkyl)-phosphine or -phosphine oxide as ligand.For butadiene conversions of from 4 to 63%, the selectivity of theformation of (1) can be increased to 66%, and for butadiene conversionsbelow 2% (i.e. large butadiene excesses) up to as much as 85%. Theselectivity of the formation of (2) is in the range from 1 to 40%, therebeing no direct relation of selectivities of the formation of (1) and(2). For example, (2) is obtained with a selectivity of 9% when (1) isproduced with a selectivity of 85%, and a selectivity of 1% when (1) isformed with a selectivity of 55%. The reaction mixtures are not workedup here either.

There is therefore a continued need for a process for preparingocta-2,7-dienyl-1-amine in good selectivities and yields as far aspossible irrespective of the catalysts, butadiene excesses and otherparameters used.

SUMMARY OF THE INVENTION

We have now found a process for the preparation ofocta-2,7-dienyl-1-amine by telomerization of butadiene with ammonia in atwo-phase system in the presence of hydrophilic palladium catalysts,which is characterized in that octa-2,7-dienyl-1-amine andocta-1,7-dienyl-3-amine are isolated separately from one another fromthe reaction mixture present after telomerization, and theocta-1,7-dienyl-3-amine isolated in this way is subjected to anisomerization reaction to form octa-2,7-dienyl-1-amine.

DETAILED DESCRIPTION OF THE INVENTION

Ammonia can be used in any desired form. Preference is given to usingmixtures of ammonia and water, for example from 5 to 35% by weightstrength aqueous ammonia solutions, or pure ammonia (commerciallyavailable product).

The two-phase system generally consists of a hydrophilic and ahydrophobic phase. The hydrophilic phase may contain, as essentialcomponent, for example water or a hydrophilic solvent or a mixture ofhydrophilic solvent and water. The hydrophilic solvent may, for examplebe C₁ -C₆ -mono-, di-, tri-, tetra-, penta- and hexaalcohols,tetramethylene sulphone, dimethyl sulphoxide or acetonitrile. Thehydrophilic phase is preferably water which can be used, for example, assuch and/or in the form of aqueous solutions of ammonia.

The hydrophobic phase can comprise, as essential component, excessbutadiene and/or an organic solvent which is immiscible or virtuallyimmiscible with water. Suitable organic solvents which are immiscible orvirtually immiscible with water are, for example, those which, at 20°C., dissolve in 100 g of water only in amounts less than 5 g, inparticular less than 3 g. Examples of such solvents are chlorinatedaliphatic and aromatic hydrocarbons, ethers, tert-amines, pyrrolidoneand aliphatic and aromatic hydrocarbons which are liquid under thereaction conditions. The hydrophobic phase is preferably butadiene,benzene, toluene or methylene chloride, in particular butadiene.

If it is desired to use butadiene as a reactant and as essentialcomponent of the hydrophobic phase, it can be used (based on 1 mol ofammonia) in amounts of at least 0.5 mol, for example. This amount ispreferably from 0.7 to 100 mol, in particular from 3 to 50 mol. Ifbutadiene is only used as reactant, it can be used (based on 1 mol ofammonia) in amounts of from 0.5 to 20 mol, preferably from 0.7 to 5 mol,for example.

Suitable hydrophilic palladium complexes are, for example, those of theformula (I)

    [L.sup.1.sub.x L.sup.2.sub.y Pd].sub.m.sup.p.sup.+ [A].sub.n.sup.q-(I),

in which

L¹ are identical or different ligands from the group consisting of asulphonated, carboxylated and hydroxylated trialkyl- andtriphenylphosphines and -phosphine oxides,

L² are identical or different ligands from the group consisting of H,CO, NO, NH₂, NH₃, PF₃, H₂ O, S, halogens, aromatic ligands, olefinicligands, allylic ligands and acetylenic ligands,

x is an integer from zero to 6, and

y is zero or an integer from 1 to 5,

the sum x+y being at least 1 and at most 6, and

m is 1, 2 or 3 and

n, p and q are in each case zero, 1, 2 or 3,

the relationship

    m·p=n·q being applicable, and

A is an anion with charge q.

Suitable ligands L¹ are preferably, mono-, bis- and tri(hydroxy-C₁ -C₅-alkyl)-phosphines, mono-, bis- and tri(hydroxy-C₁ -C₅ -alkyl)-phosphineoxides, mono-, di- and trisulphonated triphenylphosphines in acid formand mono-, di- and trisulphonated triphenylphosphines in salt form. Inparticular, sulphonated triphenylphosphine ligands may also containfurther substituents on the phenyl ring, for example, pertriphenylphosphine unit, from 1 to 3 identical or different halogenatoms and/or from 1 to 3 identical or different C₁ -C₁₀ -alkyl groupsand/or from 1 to 3 identical or different C₁ -C₁₀ -alkoxy groups.

Particularly preferred ligands L¹ are tri(hydroxy-C₁ -C₅-alkyl)-phosphines having a terminal arrangement of the hydroxyl groupson the alkyl radicals, triphenylphosphine trisulphonic acids and saltsthereof, and triphenylphosphine mono-, di- and trimethoxytri(sodiumsulphonic acids) and salts thereof, and triphenylphosphine mono-, di-and trifluoromono-, di- and trisulphonic acids and salts thereof.

Alkyl groups of triphenylphosphine units preferably contain C₁ -C₄-alkyl radicals and alkoxy groups present there, preferably C₁ -C₄-alkoxy radicals.

Very particularly preferred ligands L¹ aretris(hydroxy-3-propyl)-phosphine and the trisodium salt of3,3',3"-phosphinetriyl-tris-(benzenesulphonic acid), called TPPTS below,the trisodium salt of 3,3',3"-phosphinetriyl-bis(benzenesulphonicacid)-mono(4-methoxybenzenesulphonic acid), called MOM-TPPTS below, thetrisodium salt of 3,3',3"-phosphinetriyl mono(benzenesulphonicacid)-bis-(4-methoxybenzenesulphonic acid), called BOM-TPPTS below, thetrisodium salt of 3,3',3"-phosphinetriyl-tris(4-methoxybenzenesulphonicacid), called TOM-TPPTS below, the trisodium salt of3,3',3"-phosphinetriyl-tris-(4-methylbenzenesulphonic acid), calledTOT-TPPTS below, the trisodium salt of5,5',5"-phosphinetriyl-tris-(2-fluorobenzenesulphonic acid), calledp-F-TPPTS below, and the disodium salt of5,5'-(4-fluorophenylphosphinediyl)-bis-(2-fluorobenzenesulphonic acid),called p-F-TPPDS below.

Suitable ligands L² are, preferably, NH₂, NH₃, Cl, Br, I, allyl,methallyl, cyclopentadienyl, cyclooctadienyl and dibenzylidenacetone.

In formula (I), x is preferably zero or an integer from 1 to 4, inparticular an integer from 1 to 4, y is preferably zero, 1 or 2, the sumx+y being at most 4.

The anion A is preferably acetate, chloride, acetylacetonate,tetrafluoroborate and hexafluoroantimonate.

MOM-TPPTS and BOM-TPPTS are novel compounds. These conform in particularto the formulae (II) and (III) ##STR1## and are also provided by thepresent invention. They can be prepared as described in Angew. Chemie107, 893 (1995).

The use of TOM-TPPTS, TOT-TPPTS, p-F-TPPTS and p-F-TPPDS as ligand forthe preparation of palladium complexes for the telomerization ofbutadiene with ammonia is also novel and provided by the presentinvention. Such compounds can be prepared as described in Angew. Chemie107, 893 (1995) or J. prakt. Chem. 336, 591 (1994).

The preparation of the hydrophilic palladium complexes of the formula(I) can be carried out in a simple manner, for example by adding ligandsof type L¹ and/or of type L² to an initial charge of a palladium salt ora palladium complex compound and water. This then gives an aqueoussolution of the hydrophilic palladium complex of the formula (I), whichcan be used as such in the process according to the invention; it is,however, also possible to isolate the corresponding complexes of theformula (I) and then use the isolated complexes in the process accordingto the invention.

It is also possible to prepare hydrophilic palladium complexes of theformula (I) in situ, for example by initially introducing a palladiumsalt or a palladium complex compound together with water or aqueousammonia solution into an autoclave, then adding butadiene, the desiredligands and optionally further aqueous ammonia solution and then settingthe pressure and temperature conditions desired for the telomerization.In this case, it is possible, for example, to use 0.1-50 mol of thedesired ligand per mole of palladium salt or palladium complex compoundused. This amount is preferably 0.2-30 mol, in particular 0.3-10 mol. Inthe in-situ preparation of complexes of the formula (I), mixtures ofdifferent individual substances of the formula (I) may also form, whichare then effective, even in the form of such mixtures, as catalysts forthe process according to the invention.

Starting compounds for the preparation of hydrophilic palladiumcomplexes which are to be used according to the invention are, forexample, the following palladium salts and complexes: palladium(II)acetate, chloride, acetylacetonate, hexafluoroantimonate andtetrafluoroborate, and allyldiaminopalladium(II) tetrafluoroborate,bis-(η3-allyl-iodo)-palladium(II), allyldiaminopalladium(II)hexafluoroantimonate and any other palladium(II) salts or complexes ofthis type. The choice of palladium salts or complexes for thepreparation of hydrophilic palladium complexes of the formula (I) is ofno particular significance for the process according to the invention.The starting compounds for the preparation of hydrophilic palladiumcomplexes to be used according to the invention are also palladium(O)complexes, e.g. those of the formula

    PdL.sup.1.sub.x'                                           (IV)

in which

L¹ is as defined for formula (I), and

x' is an integer from 1 to 6.

or palladium dibenzylideneacetone.

It is also possible that the oxidation stage of the hydrophilicpalladium complex changes whilst the process according to the inventionis being carried out.

Per liter of hydrophilic phase, it is possible to use, for example, from0.5 to 500 millimol of hydrophilic palladium complexes. This amount ispreferably from 1 to 25 millimol, in particular from 2.5 to 10 millimol.If the hydrophilic palladium complexes are prepared in situ, then, forexample, from 0.5 to 500 millimol of palladium salt or palladium complexcompound are used per liter of hydrophilic phase. This amount ispreferably from 1 to 25 millimol, in particular from 2.5 to 10 millimol.

The use of catalysts of the formula (I) in which L¹ is a compound of theformula (II) or (III) or is TOM-TPPTS or TOT-TPPTS gives reactionmixtures which contain relatively high contents ofocta-2,7-dienyl-1-amine. It is, however, also possible to obtain evenmore octa-2,7-dienyl-1-amine if the octa-1,7-dienyl-3-amine alsoobtained, in relatively small amounts, is isolated and isomerized togive octa-2,7-dienyl-1-amine. The use of catalysts of the formula (I) inwhich L¹ is P-F-TPPTS and p-F-TPPDS generally leads to an increasedactivity of the catalyst.

The telomerization reaction of butadiene with ammonia can be carriedout, for example, at temperatures in the range from 30 to 150° C. andpressures in the range from 1 to 30 bar. The reaction is preferablycarried out at from 50 to 120° C. and in an autoclave under theautogenous pressure at the corresponding reaction temperature.

The telomerization reaction is generally complete after from 30 minutesto 20 hours. It is advantageous to ensure that the reaction mixture isthoroughly mixed during the reaction.

The reaction mixture can be worked up and the octa-2,7-dienyl-1-amineand octa-1,7-dienyl-3-amine present therein isolated separately asfollows, for example:

If butadiene has been used as essential constituent of the hydrophobicphase, then butadiene which is present in excess escapes when the systemis decompressed to atmospheric pressure. Residual butadiene whichremains in the reaction mixture can, if necessary, be blown out, e.g.with nitrogen. This then gives an aqueous phase containing the catalystand an organic phase containing the reaction products, which can beworked up, following separation, as described below. It is advantageousto extract the hydrophilic phase with a suitable solvent, and then toadd the extracted phase to the hydrophobic phase for combined work-up.

If an organic solvent has been used to form the hydrophobic phase, thehydrophobic phase can be separated from the hydrophilic phase, and theseparated-off hydrophilic phase can, if necessary, be washed with awater-immiscible solvent, and the wash liquid added to the hydrophobicphase.

The hydrophilic phase containing the catalyst can be used as desired,e.g. in the next batch for the preparation according to the invention ofocta-2,7-dienyl-1-amine (1) or for the isomerization of isolatedocta-1,7-dienyl-3-amine (2).

It is possible to subject the hydrophobic phase, if necessary after thesolvent present has been stripped off, and if necessary after afree-radical scavenger (e.g. a sterically hindered phenol) has beenadded, to fractional distillation. At pressures of, for example, from 4to 40 mbar, the boiling points of (1) and (2) are sufficiently differentfrom each other to allow them to be readily separated from one anotherin columns having, for example, from 50 to 150 theoretical plates and atreflex ratios of, for example, 3:1 to 15:1. In this way, it is possibleto obtain a first fraction which contains (2) and a second fractionwhich contains (1), each in purities up to 99% and above. The substanceswhich remain are relatively high boiling constituents, in particularbis-octadienylamines.

Up to this process step, it is possible to obtain (1) in selectivities(based on reacted butadiene) of, for example, from 40 to 87% and (2) inselectivities (based on reacted butadiene) of, for example, from 7 to40%.

According to the invention, the selectivity of the formation of (1) isthen increased by, for example, from 1 to 25% (based on the originalselectivity) when (2) obtained as described above is subjected to anisomerization reaction to form (1).

This isomerization can be carried out in analogous manner to thetelomerization described above, i.e. using the same catalyst and in atwo-phase system. For the isomerization, it is advantageous to use thecatalyst, or solution thereof, separated off during work-up of thetelomerization mixture. In contrast to the parameters given above forthe telomerization, it is advantageous to carry out the isomerizationunder the following conditions:

Per liter of hydrophilic phase, it is possible to use, for example, from0.5 to 500 millimol of hydrophilic palladium complexes. This amount ispreferably from 1 to 25 millimol, in particular from 2.5 to 10 millimol.It is also possible to use the hydrophilic palladium complexes in situ,for example by initially introducing a palladium salt or a palladiumcomplex compound together with water or an aqueous ammonia solution andadding the desired ligand. In this case, it is possible to use, forexample, from 0.5 to 500 millimol of palladium salt or palladium complexper liter of hydrophilic phase. This amount is preferably from 1 to 25millimol, in particular from 2.5 to 10 millimol. Per mole of palladiumsalt or palladium complex compound used, it is possible to use 0.1-50mol of the desired ligand. This amount is preferably 0.2-30 mol, inparticular from 0.3 to 10 mol.

The essential component of the hydrophilic phase can, for example, bewater or a hydrophilic solvent or ammonia. It is also possible to useany desired mixtures of water, hydrophilic solvents and ammonia. Thepresence of ammonia is always preferable. The hydrophilic solvents are,for example, C₁ -C₆ mono-, di-, tri-, tetra-, penta- and hexaalcohols,tetramethylenesulphone, dimethyl sulphoxide or acetonitrile. Thehydrophilic phase is preferably water, ammonia and mixtures of water andammonia having an ammonia content of from 1 to 99% by weight. Particularpreference is given to an ammonia content of from 5 to 60% by weight.Very particularly preferably, the ammonia content is from 10 to 30% byweight. Per liter of hydrophilic phase, it is possible to use, forexample, from 10 to 5000 g of octa-1,7-dienyl-3-amine (2). Preference isgiven to using from 50 to 3000 g, and particular preference to from 100to 2000 g, of octa-1,7-dienyl-3-amine.

The temperature is, for example, from 20 to 200° C., preferably from 40to 150° C. and particularly preferably from 60 to 120° C.

The pressure is, for example, from 0 to 500 bar. The process ispreferably carried out at a pressure of from 0 to 100 bar, particularlypreferably at the pressure which automatically results at the particulartemperature. It is also possible to carry out the reaction in anapparatus in which atmospheric pressure prevails as a result of pressurecompensation with the surroundings.

The reaction time is generally from 1 hour to 14 days and depends on theratio of octa-1,7-dienyl-3-amine (2) relative to the palladium salt orpalladium complex used and the desired degree of isomerization. It isadvantageous to ensure that the reaction mixture is thoroughly mixedduring the reaction.

The reaction mixture which remains when isomerization is complete can beworked up in the same way as the reaction mixture which remainsfollowing telomerization, for example by phase separation, extraction ofthe aqueous phase by an organic solvent and subsequent distillation ofthe combined organic phases.

It is also possible to carry out the isomerization several timessuccessively with the (2) separated off from the preceding stage in eachcase.

The invention is further described in the following illustrativeexamples. All percentages are by weight, unless otherwise noted.

EXAMPLES Example 1

4.38 g of boric acid are dissolved completely in 41 ml of concentratedsulphuric acid in a 500 ml three-necked flask under an argon atmosphere(argon is passed through the sulphuric acid beforehand in order to freeit from oxygen), 5 g of (ortho-methoxyphenyl)diphenylphosphine are thendissolved therein, and the mixture is cooled to -10° C. with anice/sodium chloride mixture. At this temperature, 73.9 ml of oleum areadded dropwise over a period of 2 h, and the solution is then stirredfor 3 h at room temperature.

Before the synthesis is continued with the hydrolysis, a 5 ml sample isfirstly taken and worked up in the same way as is described below forthe entire mixture. A ³¹ P-NMR spectroscopic investigation of thissample provides information as to whether the sulphonation has alreadyproceeded to completion. If the reaction times are too short, mono- anddisulphonated product is still present, and if the reaction times aretoo long, phosphine oxide is present. These impurities are as a wholevery difficult to remove.

For hydrolysis, 50 ml of oxygen-free water are added very slowly withice cooling. The mixture is then transferred to a 21 Schlenk flask andneutralized there with 7.5 molar sodium hydroxide solution with icecooling. It is advisable to adjust the pH to 7 as accurately as possibleusing a pH electrode. The solution is then evaporated to dryness on arotary evaporator, and then the product is extracted with 250 ml ofmethanol. The solution is filtered over Celite®, and methanol isdistilled off under reduced pressure. The residue is taken up in 20 mlof water and the mixture is filtered through a syringe filter, and thewater is removed under reduced pressure. Alternating extraction withmethanol and water gives MOM-TPPTS as trihydrate in a purity of 93% anda yield of 14%.

    ______________________________________                                        .sup.31 -NMR (D.sub.2 O):                                                                -14.6 ppm                                                            .sup.1 -NMR (D.sub.2 O): 3.6 ppm (3H); 6.96 ppm (1H); 7.02 ppm (1H);                     7.3 ppm (2H); 7.4 ppm (2H); 7.6 ppm (2H);                           7.7 ppm (3H)                                                                 .sup.13 C-NMR (D.sub.2 O): 164.2 ppm; 144.6 ppm; 138.1 ppm;                    137.06 ppm; 137.1 ppm; 132.25 ppm;                                            131.9 ppm; 131.2 ppm; 130.8 ppm;                                              128.2 ppm; 125.7 ppm; 112.9 ppm; 57.7 ppm                                  ______________________________________                                    

Example 2

The synthesis of BOM-TPPTS is carried out in an entirely analogousmanner as described in Example 1, but usingbis(ortho-methoxyphenyl)-phenylphosphine instead of(ortho-methoxyphenyl)diphenylphosphine. BOM-TPPTS is obtained as thetrihydrate in 92% purity with a yield of 14%.

    ______________________________________                                        .sup.31 -NMR (D.sub.2 O):                                                                -24.34 ppm                                                           .sup.1 H-NMR (D.sub.2 O): 3.6 ppm (6H); 7.0 ppm (2H); 7.03 ppm (2H);                     7.3 ppm (1H); 7.4 ppm (1H); 7.6 ppm (1H);                           7.7 ppm (3H)                                                                 .sup.13 C-NMR (D.sub.2 O): 161.7 ppm; 141.9 ppm; 135.5 ppm;                    134.4 ppm; 133.55 ppm; 129.6 ppm;                                             129.4 ppm; 128.5 ppm; 128 ppm;                                                125.6 ppm; 121.8 ppm; 110.3 ppm; 55 ppm                                    ______________________________________                                    

Example 3

1372 g of bis(³ η-allyl-iodopalladium) are dissolved in 10 ml of anaqueous 27% strength NH₃ solution. This solution is added to a solutionof 973.4 mg of AgBF₄ in 5 ml of water. The Agl which precipitates out isthen filtered off over Celite®. The filtrate is reduced by evaporation,and the product is dissolved out of the residue by triple extractionwith 10 ml of boiling CH₂ Cl₂ in each case, and this solution is in eachcase decanted off. Some of the product precipitates out merely uponcooling, and the remainder is precipitated out by adding 20 ml ofpentane. The white solid is washed three times with 5 ml of pentane ineach case and dried under a high vacuum. [³η-Allyl-diaminopalladium]tetrafluoroborate is obtained in a yield of50.3%.

¹ H-NMR (D₂ O): 2.9 ppm (2H); 4.0 ppm (2H); 5.5 ppm (1H) ¹³ C-NMR (D₂O): 61 ppm; 118 ppm

Example 4

The reaction is carried out in a stainless steel autoclave having avolume of 125 ml which contains a stirring system comprising a 6-bladedisc agitator in combination with flow disruptors, and is heatedelectrically. The autoclave is initially assembled, and evacuated threetimes to remove the oxygen and filled with argon.

30.3 mg of [³ η-allyl-diaminopalladium]tetrafluoroborate are weighedinto a Schlenk tube and, together with 15 ml of an aqueous 27% strengthammonia solution, transferred to the autoclave. 40 g of butadiene arethen introduced via a metering cartridge. The contents of the reactorare heated to 80° C. with stirring (2000 rpm). Meanwhile, 0.113 mmol ofTPPTS in the form of a 32.4% aqueous solution are weighed into a Schlenktube and, together with 15 ml of an aqueous ammonia solution,transferred to a steel dropping funnel. The latter is assembled on theautoclave. At an internal temperature of 80° C., the pressurecompensation is firstly opened, followed by the tap of the droppingfunnel. The temperature drops to about 60° C., but within 3 min againreaches the desired value of 80° C. After a reaction time of 45 min, theautoclave is placed into an icebath and, with the speed of the stirrerreduced (200 rpm), the excess butadiene is blown off using a Bunsenburner. In this way, the contents of the reactor cool to 20° C. over thecourse of 5 min. When all of the butadiene has been burned off, theautoclave is opened and the contents transferred to a separating funnel.Rinsing is then carried out with 10 ml of toluene, followed byextraction, and a spatula tip of sodium chloride is added to acceleratephase separation. Following phase separation, the GC standard undecaneis weighed into the organic phase, which is dried over a 4 Å molecularsieve. The molecular sieve is then filtered off and washed with 10 ml oftoluene. A sample is taken, and the composition is investigated usinggas chromatography. The conversion in terms of butadiene was 5.8%. Thecomposition of the sample was 76% of (1), 21% of (2) and 3% of (3).

Examples 5 to 7

The procedure is identical to that described in Example 4. However,instead of 0.113 mmol of TPPTS, other amounts of this compound are used.The examples are listed in Table 1:

                  TABLE 1                                                         ______________________________________                                                Amount     Conversion Composition                                       Example of (based on (% by weight)                                          No.     TPPTS      butadiene) (1)  (2)   (3)                                  ______________________________________                                        5       0.226 mmol 15.5%      50   35    12                                     6 0.452 mmol  7.0% 51 43 4                                                    7 0.678 mmol  0.9% 48 50 0.5                                                ______________________________________                                    

Examples 8 to 11

The procedure is identical to that described in Example 4. However,instead of an aqueous solution of TPPTS, MOM-TPPTS is used in the formof the trihydrate. The amounts of this compound used are likewisevaried. The examples are listed in Table 2:

                  TABLE 2                                                         ______________________________________                                                Amount     Conversion Composition                                       Example of (based on (% by weight)                                          No.     MOM-TPPTS  butadiene) (1)  (2)   (3)                                  ______________________________________                                         8      0.113 mmol 6%         70   22    7                                       9 0.226 mmol 16.5% 49 40 8                                                   10 0.452 mmol 13.4% 40 37 8                                                   11 0.678 mmol  5.2% 42 40 2.2                                               ______________________________________                                    

Examples 12 to 15

The procedure is identical to that described in Example 4. Instead ofusing an aqueous solution of TPPTS, BOM-TPPTS in the form of itstrihydrate is used. The amounts of this compound used are likewisevaried. The examples are listed in Table 3:

                  TABLE 3                                                         ______________________________________                                                Amount     Conversion Composition                                       Example of (based on (% by weight)                                          No.     BOM-TPPTS  butadiene) (1)  (2)   (3)                                  ______________________________________                                        12      0.113 mmol 2.9%       87    7    5                                      13 0.226 mmol 6.5% 65 17 0.3                                                  14 0.452 mmol 8.0% 58 33 7                                                    15 0.678 mmol 9.3% 53 33 7                                                  ______________________________________                                    

Examples 16 to 19

The procedure is identical to that described in Example 4. Instead ofusing an aqueous solution of TPPTS, TOM-TPPTS in the form of itstrihydrate is used. The amounts of this compound used are likewisevaried. The examples are listed in Table 4:

                  TABLE 4                                                         ______________________________________                                                Amount     Conversion Composition                                       Example of (based on (% by weight)                                          No.     TOM-TPPTS  butadiene) (1)  (2)   (3)                                  ______________________________________                                        16      0.113 mmol 1.05%      94   3     1                                      17 0.226 mmol 2.25% 94 3.5 1.2                                                18 0.452 mmol 2.3% 87 4 3                                                     19 0.678 mmol 2.3% 89 7 3                                                   ______________________________________                                    

Examples 20 to 22

The procedure is identical to that described in Example 4. However,instead of using an aqueous solution of TPPTS, TOT-TPPTS in the form ofits trihydrate is used. The amounts of this compound used are likewisevaried. The examples are listed in Table 5:

                  TABLE 5                                                         ______________________________________                                                Amount     Conversion Composition                                       Example of (based on (% by weight)                                          No.     TOT-TPPTS  butadiene) (1)  (2)   (3)                                  ______________________________________                                        20      0.113 mmol 1.05%      91   5     1                                      21 0.339 mmol 3.3% 86 4 8                                                     22 0.678 mmol 2.7% 90 5 3                                                   ______________________________________                                    

Example 23

The procedure is identical to that described in Example 4. However,instead of using an aqueous solution of TPPTS, 2.428 mmol of TOM-TPPTSin the form of the trihydrate and 0.971 mol of [³η-allyl-diaminopalladium]tetrafluoroborate are used. The conversion interms of butadiene was 29.0%. The composition of the sample is 67% byweight of (1), 13% by weight of (2) and 17% by weight of (3).

Example 24

The procedure is identical to that described in Example 18. However, inthis case a reaction time of 7 hours is maintained. The conversion interms of butadiene was 30.4%. The composition of the sample is 78% byweight of (1), 5% by weight of (2) and 16% by weight (3).

Example 25

The procedure is identical to that described in Example 4. However,instead of using an aqueous solution of TPPTS, a mixture of 0.099 mmolof p-F-TPPDS in the form of the dihydrate and 0.015 mmol of p-F-TPPTS inthe form of the trihydrate is used. The conversion in terms of butadienewas 8.2%. The composition of the sample is 54% by weight of (1), 38% byweight of (2) and 6% by weight of (3).

Examples 26 to 29

The procedure is identical to that described in Example 4. However,instead of [³ η-allyl-diaminopalladium]tetrafluoroborate, otherpalladium compounds are used. In addition, the amount of TPPTS used wasvaried. The examples are listed in Table 6:

                  TABLE 6                                                         ______________________________________                                                          Amount    Conversion                                                                            Composition                                 Example Palladium of (based on (% by weight)                                No.    compound   TPPTS     butadiene)                                                                            (1) (2) (3)                               ______________________________________                                        26     Palladium  0.339 mmol                                                                              15.7%   53  35  6                                    acetate                                                                      27 Palladium bis- 0.339 mmol 11.3% 53 40 6                                     (diacetylace-                                                                 tonate)                                                                      28 Palladium 0.339 mmol 14.2% 54 39 6                                          chloride                                                                     29 Bis-(.sup.3 η-allyl- 0.226 mmol 13.5% 58 32 9                           iodo-                                                                         palladium)                                                                 ______________________________________                                    

Example 30

A solution of 1.5 mmol of palladium acetate and 4.5 mmol of TPPTS (TPPTSis used in the form of a 32.4% strength aqueous solution) in 250 ml of a20% strength aqueous ammonia solution is introduced, in an argoncounterflow, into a stainless steel autoclave which has been evacuatedthree times beforehand and filled with argon. 120 g of butadiene arecondensed and the autoclave is heated to 80° C. with vigorous stirringover a period of 15 min. The reaction mixture is vigorously mixed atthis temperature for a further 45 min. Heating is then stopped and theexcess butadiene is burned off using a Bunsen burner. As a result, thecontents of the autoclave cool. When all of the butadiene has beenburned off, the contents of the autoclave are transferred to aseparating funnel and then phases are separated. The aqueous phase isextracted 3 times with 40 ml of pentane in each case, and this extractis combined with the organic phase. The water which is eliminated in theprocess is separated off and discarded. The residual organic phase isdried over a molecular sieve. The drying agent is separated off and thesolvent is removed on a rotary evaporator. The residual liquid is mixedwith 2 g of 2,4-di-tert-butylphenol and subjected to fractionaldistillation. A column with 80 theoretical plates and a reflux ratio of1:10 is used. At a pressure of 20 mbar and a head temperature of 61° C.34.1 g of compound (2) are isolated. Likewise at 20 mbar and a headtemperature of 75.5° C., 55 g of compound (1) are isolated.

The total amount of compound (2) is transferred for isomerization to aglass autoclave together with 0.974 mmol of palladium acetate, 5.58 mlof TPPTS (in the form of a 32.4% strength aqueous solution) and 290 mlof a 27% strength ammonia solution. The mixture is stirred vigorouslyfor 15 hours at a temperature of 80° C. and then cooled to roomtemperature. The phases are separated, the aqueous phase is extractedwith a total of 50 ml of pentane, and the extracts are combined with theorganic phase. The water which is eliminated is separated off anddiscarded. The organic phase is dried over a molecular sieve, the dryingagent is separated off and the solvent is removed on a rotaryevaporator. The residue is, as already described above, subjected tofractional distillation. This gives 19.8 g of compound (2) and 6.5 g ofcompound (1). The total amount of compound (2) is again subjected to anisomerization reaction and subsequent separation by distillation in amanner which is entirely analogous to that described above. This gives3.6 g of compound (1) and 11.5 g of compound (2). The total amount ofcompound (2) is in turn subjected to an isomerization reaction andsubsequent separation by distillation in a manner which is entirelyanalogous to that described above. This gives 1.8 g of compound (1) and6.1 g of compound (2).

Altogether, the telomerization with subsequent triple isomerizationdescribed here gives 66.9 g of compound (1), which corresponds to aconversion of 48.2% in terms of butadiene.

Examples 31 and 32

The experiments for recycling the catalyst phase were carried out in astainless steel autoclave having a volume of 125 ml, which contains astirring system comprising a 6-blade disc agitator in combination withflow disruptors and which is heated electrically. The autoclave isinitially assembled and evacuated three times to remove the oxygen andfilled with argon.

25.4 mg of palladium acetate and the corresponding amount of TPPTS areweighed into a Schlenk tube. The catalyst transferred to the autoclavetogether with 30 ml of a 27% strength aqueous NH₃ solution. 40 g ofbutadiene are then condensed, and the autoclave is heated to thereaction temperature (80° C.) with stirring. The heating phase lasts 25min. After this heating phase, the reaction temperature is maintainedfor a further 50 min. The autoclave is then placed into an icebath andthe butadiene is blown off using a Bunsen burner. As a result, theinternal temperature drops to 20° C. within 5 min. When all of thebutadiene has been burned off, the contents of the reactor aretransferred, via a riser pipe which extends to the floor inside theautoclave, to a protective-gas separating funnel. For this, argon is fedonto the autoclave at a pressure of 0.5 bar via the needle valve, thispressing out the liquid via the riser pipe. In the separating funnel,the phases are separated and the catalyst phase is transferred back tothe autoclave. 1 g of ammonia and 40 g of butadiene are then condensedin the autoclave. The procedure from here is the same as that alreadydescribed for the first run. A total of 4 runs are carried out with thesame catalyst phase. The organic phases are admixed with 10 ml oftoluene, and the GC standard undecane is weighed in. The phases are thendried over 4 Å molecular sieve and the composition is determined by gaschromatography. The results are listed in Tables 7 and 8.

                  TABLE 7                                                         ______________________________________                                        Example 31:0.339 mmol of TPPTS were used                                                 Conversion                                                                              Composition                                                (based on (% by weight)                                                              butadiene)                                                                            (1)       (2)   (3)                                          ______________________________________                                        Run 1      17.6%     55        37   7                                           Run 2 14.3% 53 36 10                                                          Run 3 12.9% 53 31 15                                                          Run 4  5.9% 54 28 16                                                        ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Example 32:0.565 mmol of TPPTS were used                                                 Conversion                                                                              Composition                                                (based on (% by weight)                                                              butadiene)                                                                            (1)       (2)   (3)                                          ______________________________________                                        Run 1      4.3%      50        45  3                                            Run 2 6.6% 49 43 5                                                            Run 3 9.2% 47 40 8                                                            Run 4 8.1% 46 41 7                                                          ______________________________________                                    

Example 33

The procedure is as described in Examples 31 and 32 but using TOM-TPPTSinstead of TPPTS. A weighed amount of TOM-TPPTS corresponded to anamount of 0.565 mmol. The reaction time was 200 minutes. The result ofthe experiment is given in Table 9.

                  TABLE 9                                                         ______________________________________                                                 Conversion                                                                            Composition                                                    (based on (% by weight)                                                              butadiene)                                                                            (1)       (2)   (3)                                          ______________________________________                                        Run 1      7.7%      88        45  6.5                                          Run 2 10.7% 85  5 10                                                          Run 3 9.6% 77  5 16                                                           Run 4 8.3% 75  5 17                                                         ______________________________________                                    

Although the invention has been described in detail in the foregoing forthe purpose of illustration, it is to be understood that such detail isfor that purpose and that variations can be made therein by thoseskilled in the art without departing from the spirit and scope of theinvention.

What is claimed is:
 1. A sodium salt of3,3',3"-phosphinetriyl-bis-(benzenesulphonicacid)-mono-(4-methoxybenzenesulphonic acid) comprising the formula II##STR2##
 2. A sodium salt of3,3',3"-phosphinetriylmono-(benzenesulphonicacid)-bis(4-methoxy-benzenesulphonic acid) comprising the formula (III)